US3343373A

US3343373A - Two-phase thermo-electric body comprising a boron-carbon matrix

Info

Publication number: US3343373A
Application number: US283487A
Authority: US
Inventors: Courtland M Henderson; Jr Emil R Beaver
Original assignee: Monsanto Co
Current assignee: Monsanto Co
Priority date: 1963-05-27
Filing date: 1963-05-27
Publication date: 1967-09-26
Anticipated expiration: 1984-09-26

Description

Sept. 26,- 1-967 'c. M. HENDERSON ETAL 3,343,373

TWO-PHASE THERMQ-ELECTRIC BODY COMPRISING A BORON-CARBON MATRIX Filed May 27, 1963 2 Sheets-Sheet l g oL ZONE 'COLD HOT 22 FIGURE 1 Lia "I:

HOT ZONE wia N AND "P" TYPE MATERIAL (6O 7' OF MATRIX MELTING POINT) MOLE70 MOLE MOE YoY FIGURE 4 9? E555 4 32 l m s 0 Li G E I v o n.

FIGURE 7 INVENTQRS W COURTLAND M. HENDERSON EMIL R. BEAVER,J'R. BY

Sept. 26, 1967 c. HENDERSON ETAL 3,343,373

TWO-PHASE THERMO-ELECTRIC BODY COMPRISING A BORON-CARBON MATRIX Filed May 27. 1963 2 Sheets-Sheet 2 xxxx' :N" A N D TYPE MATERIA LS TIME TEMPERATURE HRS.

FIGURE 6 TEM PE RATU RE "6 INVENTORS Fl GU R E 5 COURTLAND M. HENDERSON EMIL R. BEAVER,JR.

MQW M United States Patent' 3,343,373 TWO-PHASE THERMO-ELECTRIC BODY COM- PRISING A BORGN-CARBON MATRIX Courtland M. Henderson, Xenia, and Emil R. Beaver, Jr.,

Tipp City, Ohio, assiguors to Monsanto Company, a

corporation of Delaware Filed May 27, 1963, Ser. No. 283,487 11 Claims. (Cl. 62-3) This application is a continuation-in-part of copending applications, Ser. No. 169,501, now U.S. Patent No. 3,256,- 700; No. 169,283, now U.S. Patent No. 3,256,698; No.

169,536, now U.S. Patent No. 3,256,701; No. 169,395,

now U.S. Patent No. 3,256,699; No. 169,209, now U.S. Patent No. 3,256,696; No. 169,210, now U.S. Patent No. 3,256,697 and No. 169,579, now U.S. Patent No. 3,256,- 702; all filed Jan. 29, 1962.

The present invention relates to thermoelectricity, novel thermoelectric materials and elements thereof and processes for their manufacture. It is an object of the invention to provide greatly improved thermoelectric combinations relative to presently known materials and devices. It is also an object of the invention to manufacture these novel thermoelectric elements and devices by improved processes in order to control thermoelectric and lattice strain properties thereof. It is an object of the invention to produce conditions of proper matrix strain that will not fade or be lost as rapidly when the thermoelectric material is used at high temperatures. It is a further object of the invention to provide a method for producing said thermoelectric materials in a form which will provide either for the conversion of heat into electricity or the removal of heat by electricity at efliciencies significantly greater than are presently possible with currently available thermoelectric materials and devices.

One of the greatest obstacles preventing the more widespread commercialization of thermoelectric devices is the lack of materials of suflicient effectiveness, i.e., having sufficiently high merit factors to yield cooling, heating and power generating devices of thermal efliciencies high enough to make them economically competitive with their conventional mechanical counterparts. The relation of thermoelectric parameters to Z, a merit factor of importance for heating, cooling and power generation applications, is shown below Z=S /pK where S :the Seebeck coefficient, =electrical resistivity and K thermal conductivity As is well recognized by those skilled in this art, thermoelectric materials have not yet been produced that will simultaneously exhibit high Seebeck coefiicients, low electrical resistivities and low thermal conductivities to yield high enough merit factors and efficiencies to make devices based on thermoelectricity economically competitive with conventional power generating and cooling devices.

Various routes have been followed in an attempt to overcome this obstacle. For example, attempts have been made to increase the merit factors of materials by decreasing the product of the resistitivity and thermal conductivity through increasing the mobility of the carriers (e.g., electrons and/ or holes) relative to the thermal conductivity of thermoelectric materials through the use of materials composed of atoms having large atomic weights. The top merit factors for power generation materials operating at temperatures of 700 C. and higher have been below 0.6 X 10- C.

Another popular approach has been to produce alloy type thermoelectric materials in which a homogeneous distribution of constituents in the alloy is obtained by solid solution, so as to decrease the product of the resistivity and the thermal conductivity of thermoelectric materials. This solid solution or alloy approach has resulted in less than a 10% increase in the Z merit factor for a given thermoelectric material and such materials exhibit poor mechanical properties. More important, the beneficial effect of the homogeneous distribution obtained by the alloy approach is lost after a short time when such thermoelectric materials are used at high temperatures for power generation.

Another approach has been to form physical voids or holes in a given thermoelectric material. While some slight increase in the Seebeck coefficient occasionally results from this approach, improvement in the merit factor possible through this means is usually less than 5%. The presence of voids (filled with a vacuum, air or other gas) has reduced the strength and other mechanical properties of thermoelectric materials so that serious reductions in the life and performance of devices made from such materials more than oilset the small gains in the efliciency obtained. In addition, it has been impractical to adequately control the concentration and placement of the voids to obtain the best results. Prior art has held that the presence of insoluble inclusions in the thermoelectric materials is detrimental to obtaining high Z factors.

Still another approach has been to improve the merit factors of thermoelectric materials by introducing strain into their solid state lattice structure. Such lattice strain is usually accomplished by placing the material under high stress during fabrication or by a combination of precipitating a small particle phase simultaneously with stressing the lattice during fabrication. This approach results in only a temporary improvement in power generation and heating-cooling characteristics of such materials since the precipitate phases are redissolved and the lattice strain lost when they are exposed to elevated temperatures.

The above problems are overcome and significant increases in the merit factor of thermoelectric materials is possible through the teachings of this invention. This invention follows an opposite approach from prior art teachings in that a stable compound or combination of compounds of the group of sulfides, oxides, borides, carhides, nitrides, silicides and phosphides of boron, thorium, aluminum, magnesium, calcium, titanium, zirconium, tantalum, silicon, vanadium, hafnium, columbiurn, tungsten, iron, tin, cobalt, nickel, rhenium, molybdenum, beryllium, barium, and rare earths of the lanthanide and actinide series are dispersed within the thermoelectric matrix mate-rials as set forth below. Matrices of semiconductors or thermeolectric materials of this invention, within which the above group of dispersants are distributed consist, as shown in FIGURE 4, of various combinations of boron and carbon in the range between mole percent boron and 25 mole percent carbon to 95 mole percent boron and 5 mole percent carbon. Preferred ranges of consolidated boron-carbon compositions contain from mole percent boron and 20 mole percent carbon to 93 mole percent boron and 7 mole percent carbon; still more preferred ranges being between mole percent boron and 15 mole percent carbon to 91 mole percent boron and 9 mole percent carbon.

The boron-carbon combinations exist as stoichiometric and non-stoichiometric compounds and solutions containing small or large proportions of the excess element. Such excess does nto function as a dispersant of the type described above.

The boron-carbon matrix is doped with various elements and combinations thereof to yield n and p type thermoelectric materials capable of long life at elevated temperatures. Dopants are distinguished from dispersants in that dopants are quite soluble, e.g., more than mole percent at 60% of the absolute melting point temperature of matrix, while dispersants are less soluble than this figure, e.g., or less than 10 mole percent.

It is noted that the dispersants are always present as insoluble phases, throughout the above ranges of concentration, since their solubility and chemical reactivity with the matrix are always less than the 10% limit expressed above.

Various elements and combinations thereof are used to yield n and p type thermoelectric materials capable of long life at elevated temperatures. These dopants include germanium, platinum, osmium, rubidium, rhenium, magnesium, manganese, aluminum, silicon, phosphorus, beryllium, zirconium, cobalt, nickel, thorium, titanium, tungsten, molybdenum, yttrium, calcium, and uranium present in concentrations of 1 10 mole percent to 25 mole percent as elements, or compounds of these elements, having appreciable solubility in the boroncarbon material. P-type or n-type elfects are a function of such dopants. The element, combination of elements, and the concentrations used in the formulation, for example, combinations of dopant elements to form a soluble compound (e.g., beryllium silicide) produce p type effects while the addition of the beryllium in a different combination (e.g., berillium boride) produces the opposite or n type effect.

The materials of this invention are to be distinguished from nonstoichiometric compounds or thermoelectric materials. Further, they are to be distinguished from the impurity compounds and randomly dispersed inclusions resulting from the reaction of the matrices of conventional semiconductor or thermoelectric materials with their environments, such as oxygen, during processing. The size, spacing and concentration of the dispersants of this invention in boron-carbon matrices permit significantly greater variations and control of the relation between its electrical resistivity and thermal conductivity, and to some extent the Seebeck coefiicient, than has been possible with prior art practices. This is done by causing the additive particles, which are substantially insoluble in the matrix materials, to be placed close enough to each other so as to affect the lattice structure of the matrix 3 materials by inducing strain. This impedes the flow of thermal energy, as by phonons, more than the flow of electrical charge carriers (electrons, holes, ions and other). Dispersion of such additive particles usually has a beneficial effect on the Seebeck coefficient, but the main result is to permit a long-life net decrease in the product of the resistivity and the thermal conductivity with a correspondingly long life increase in the merit factor for the aforesaid thermoelectric materials.

From the viewpoint of optimizing device performance it is also desirable to provide semiconductor or thermoelectric materials in which the resistivity and thermal conductivity can be controllably varied along energy flow paths. Ability to vary and control the thermoelectric parameters such as the Seebeck coefiicient, electrical resistivity and thermal conductivity for both p and n type materials, through use of additives or dispersants as prescribed herein produces significant and more permanent merit factor increases for the modified thermoelectric materials as compared with unmodified ones.

An additional advantage of the use of the dispersion of the presently characterized small strong particles or nuclei through the matrix of semiconductor or thermoelectric materials is the appreciable improvement of their strength and other physical properties. For example, when semiconductor materials are to be used at temperatures high enough to cause their destruction by oxidation, presence of the dispersed refractory materials in the matrix thermoelectric material improves their resistance to such attack. Further the presence of these dispersed particles enhances the bonding of ceramic type coatings, as well as the bonding of electrical and thermal leads to the thermoelectric element, since it is often possible to more readily join an oxide or refractory protective coating or heat resistant electrical and thermal leads to the improved matrix thermoelectric materials by sintering the protective coating or lead elements to the surface of the matrix material where the dispersed particles are present. For example, it is found that silicon nitride dispersed in a matrix of boron-carbon greatly improves the bonding of a protective high temperature coating of molybdenum disilicide to the matrix material.

The drawings of the present invention illustrate specific devices of the present invention, and the use thereof for interconverting heat and electrical energy, e.g., by applying one of the aforesaid forms of energy and withdrawing the other of the aforesaid forms of energy from opposed regions of a shaped body of the present modified thermoelectric materials. FIGURE 1 presents a typical cooling, heating or power generating circuit in which units of the present invention are useful. FIG- URE 2 shows a typical cooling-heating or power generating type unit in which elements made of the dispersed particle thermoelectric materials of this invention are demonstrated. FIGURE 3 shows the details of the microstructure of the compacted thermoelectric element made from the materials of this invention. FIGURE 4 presents plots of typical merit factors at two temperature ranges for various boron-carbon compositions of this invention. FIGURE 5 presents a comparison over a range of temperatures of the merit factors of prior art p and n type boron-carbon versus merit factors of the dispersed phase materials of this invention. FIGURE 6 shows that the merit factor of typical prior art p and n type boron-carbon materials decrease more rapidly with time, under high temperature power generating and cooling conditions, than the merit factors of the same composition matrix modified by the teachings of this invention. FIGURE 7 shows the critical relationship of the percent cubic thermal expansion of the dispersant and the matrix.

This invention includes a process for manufacturing thermoelectric elements of improved merit factors by inducing strain into the lattice of the semiconducting matrix materials, in order to obtain improved merit factors, by the use of refractory phases which have different coefficients of expansion than the semiconductor or thermoelectric matrix materials in which they are dispersed. This practice is most useful for power generating and high temperature heating-cooling devices in which the thermoelectric material is to be heated to high operating temperatures.

The induction of stress or strain into the matrix thermoelectric material lattice by the above method offers an additional means of preferentially causing the thermal conductivity of such matrix materials to decrease more than the resistivity increases, since the flow of heat by phonons can be preferentially impeded more than the flow of charge carriers (electrons, ions, and holes). The dispersed particles serve to lock or retain for significantly longer periods (as compared with prior art methods) of time the desired degree of strain within the matrix lattice by preventing or greatly retarding the flow of dislocations that would release such strain, or stress, within the lattice.

The present invention is based upon the use, in consolidated shaped bodies of boron and carbon of dispersants of a specific group of the above sulfides, oxides, borides, carbides, nitrides, silicides and phosphides, namely, those which have particular ranges of values for their cubic coefficients of thermal expansion. The dispersants of the present class are those having a percentage of cubic thermal expansion, up to 1500 C. which deviates from that of the matrix by sufiicient degree to make the differential thermal expansion of the dispersant (relative to that of the matrix) cause strains to be set up in both materials due to non-linear expansion and contraction with changes in temperature. These ranges lie within the cross-hatched areas established in FIG- URE 7 relating deviation in percent cubic thermal expansion between the matrix and dispersant, plotted against expansion of the matrix shown as the central horizontal axis, which is represented as a temperature scale increasing to the right. These ranges include dispersant materials whose percentage of cubic thermal expansion deviates arithmetically from that of the particular matrix by a deviation'of from 1.50% to 6.00% over the temperature range of from C. to 150 C. A more preferred range is 1.75% to 6.00% deviation, while the most preferred range is from 2.00% to 6.00% deviation.

The percentage of cubic thermal expansion referred to above is defined as the difference in volume of a dispersant material over a temperature range from 0 C. to a given higher temperature (e.=g., 1500 C.), divided by the volume of material at 0 C., and multiplied by 100. This range broadly includes materials that expand or contract volumetrically with temperature, within the limits of elasticity of the dispersant and the matrix.

As an example of the use of the above criteria the 89 mole percent B-ll mole percent C composition, having a 2.40% cubic thermal expansion over a 01500 C. range, is modified with about 1 mole percent CaO dispersant having a 6.75% cubic thermal expansion over a 0-1500 C. range. The deviation of the expansion of the dispersant from that of the matrix is 4.35%. This 4.35% falls in the 2.00% to 6.00% deviation range specified, with the resulting stresses on matrices and dispersants being well under their elastic limits. Thus by thermal expansion criteria, calcium oxide is considered to be a useful dispersant by thermal expansion criteria of the present invention.

The compositions of matter of this invention are obtained by controlling the composition to contain broadly from 0.001 mole percent to 29 mole percent of at least one small particle refractory phase, defined above, homogeneously dispersed through a matrix of boron-carbon thermoelectric material, the balance of the composition substantially being made up of the matrix material. A more preferred composition contains from 0.01 mole percent to 20 mole percent of at least one small particle refractory phase dispersed in a matrix of thermoelectric material. The most preferred composition contains from 0.1 mole percent to 15 mole percent of the small particle refractory phases dispersed through a matrix of the thermoelectric material. In general, the dispersed phase should be substantially insoluble (less than 10 mole percent at 60% of the melting point temperature, absolute, of the matrix) and otherwise meet the criteria that the melting point (absolute temperature) of the refractory phase should exceed the melting point (absolute temperature) of the matrix material in which they are dispersed, by a factor of 5%. More preferably, the melting point of the dispersed phase should exceed the melting point of the matrix material by Most preferably, the absolute melting point of the refractory dispersed phase should exceed that for the matrix by or more. Broadly, the size of the particles of the dispersed phase should be larger than 50 A. but not exceed 500,000 A. with preferred sizes ranging from 100 A. to 400,000 A. and most preferably between 200 A. and 350,000 A. Useful interparticle distances between particles of nuclei range from 50 A. to 500,000 A. A more preferred interparticle spacing of the dispersed particles in the matrix ranges from 100 A. to about 350,000 A., with the most 6 preferred interparticle spacing for optimum properties ranging from 200 A. to less than 200,000 A.

In FIG. 4, the composition of the boron-carbon matrix (exclusive of dopants) of the thermoelectric material in which the small particles are dispersed, is broadly defined to range from 75 mole percent boron (X component of FIGURE 4) and 25 mole percent carbon (Y component of FIGURE 4) to 95 mole percent boron with 5 mole percent carbon. A more preferred range of matrix composition is between mole percent boron with 20 mole percent carbon and 93 mole percent boron with 7 mole percent carbon. A most preferred range of matrix composition is between mole percent boron with 15 mole percent carbon and 91 mole percent boron with 9 mole percent carbon. Dopants of the p type for boron-carbon, such as magnesium, aluminum, and silicon in the range of 1 10 mole percent to 15 mole percent of the thermoelectric matrix are used. For n type boron-carbon, dopants such as beryllium, cobalt, and nickel in the range of 1x 10- mole percent to 25 mole percent of the thermoelectric matrix are useful.

In the following examples, the shaped bodies of the various thermoelectric compositions are formed by consolidating the particulate components; the thermoelectric units are then made by attaching leads, after which measurements are made to determine the merit factor Z with respect to cooling and power generating characteristics. The specific preferred dispersants used prevent recrystallization at high temperatures.

The following examples illustrate specific embodiments of the present invention and show various comparisons against prior art compositions and materials.

EXAMPLE 1 As a specific example of typical results obtainable through the teaching of this invention in producing superior high temperature power generating materials and devices, 14 mole percent of silicon nitride consisting of particles ranging in size from A. to 10,000 A. is homogeneously distributed through a boron (89 mole percent)-carbon (11 mole percent) p type matrix doped with 0.4 mole percent of magnesium and 0.1 mole percent aluminum so that the approximate average interparticle spacing between the silicon nitride particles in this doped matrix is 280 A. after compacting at 2050 C. and 5000 p.s.i. The Z factor of a 14 mole percent boron nitride modified boron (89 mole percent)-carbon (11 mole percent) similarly doped matrix material is 0.8 10 C. at about 1400 C. The Z factor for the modified boron-carbon matrix with dispersed silicon nitride is 0.9 10 C. at about C. or 61% of the melting point of the matrix, as shown in FIGURE 4, or about 12.5% higher than the Z factor for the boron nitride modified specimen of the same composition for the same operating temperatures, as indicated in FIGURE 4. The merit factor for a complementary n type boron (89 mole percent)-carbon (11 mole percent) doped with 18 mole percent beryllium is similarly increased from 0.5 X 10 C. to 0.7X10 C. by fabricating elements in which 14 mole percent of the same size boron nitride and silicon nitride particles, respectively, are homogeneously dispersed.

The percent cubic thermal expansion of the above matrices and dispersants, as well as the deviation between them are shown in the table below.

7 EXAMPLE 2 A specific example of typical results obtained when a conventional high temperature heating-cooling type thermoelectric material is modified by the teachings of this invention is shown with a p type boron (89 mole percent)-carbon (11 mole percent) matrix doped with 0.4 mole percent magnesium and 0.17 mole percent aluminum, modified by having dispersed within it 8 mole percent of calcium-oxide. Particle size of the calcium oxide additive ranges in size from 150 A. to 200,000 A. This composition is compacted at 1980 C. under 400 p.s.i. The resulting compacts show interparticle spacings between the additive dispersant particles varying from 200 A. to 350,000 A. The Z factor of a doped, boron nitride modified p type matrix processed in the same die at the same pressure and temperature is only 0.8 1-0- C. at 1200 C., e.g., as compared with -0.9 10" C. for the dispersed calcium oxide additive-modified but otherwise same composition matrix material when tested under the same conditions. This represents an increase of about 12.5% in the merit factor for the calcium oxide modified over the boron nitride modified boron-carbon material of the same composition.

Similarly, significant increases in the merit factors of p and n type boron carbon composition matrix materials of this invention are obtained by dispersing refractory compounds such as carbides, oxides, phosphides, borides, silicides, sulphides, and nitrides to meet the prescribed particle size and interparticle spacing conditions, ratios of the melting points of the dispersants to the melting points of the matrices, coefiicient of thermal expansion and low solubility of the dispersants in the matrix criteria.

The percent cubic thermal expansion of the dispersants and matrices and deviations between them are shown in the following table:

Various methods are used for producing the modified thermoelectric materials of this invention. In general, powder metallurgy and ceramic fabrication methods are employed. Such methods make use of fine particle powders which are compacted into final or intermediate shapes at elevated pressures and temperatures. Fine particle powders of rounded or near spherical shapes are preferred, but irregularly shaped powder particles are satisfactory. Pressure forming, as by mechanical dies, hydrostatic compaction and hot or cold extrusion followed by sintering may be used. Hot-pressing is also used, if care is taken to carry out the operation at temperatures and under protective atmospheres that will not damage the thermoelectric matrix material through harmful phase changes, melting, or loss of components through oxidation and evaporation.

One preferred method of producing the improvde thermoelectric units, characterized by homogeneous dispersion is to mechanically blend fine particle powders of predoped p and n type boroncarbon thermoelectric matrix materials with the proper proportions of an insoluble dispersant. Such blended powder is then charged into a metal die where it is compacted to a minimum of 75% of theoretical density (for any given composition) under pressures ranging from 0.25 to 200 tons per square inch. For low (less than 500 C.) temperature materials and devices, the compacted powder blend can be formed directly into a unit to which may be attached electrical and thermal leads, such as

elements

4 and 5 of FIGURE 2. The same procedure can also be used for high temperature units, but it is often more practical to attach high temperature leads in a separate action, as by spot welding or brazing.

Sintering of the compacted elements using temperatures as high as of the melting point of the matrix material improves the physical properties of the compact. In many cases, it is advantageous to attach the electrical and thermal leads to the compacted thermoelectric element during this sintering step.

High-temperature plasma spraying equipment is useful to produce modified boron-carbon thermoelectric units like element 20 of FIGURE 1 and elements 10 and 11 of FIGURE 2, having microstructures like that of FIG- URE v3.

EXAMPLE 3 Specifically, when a boron (89 mole percent) carbon (11 mole percent) powdered matrix material is mechanically blended with 4 mole percent of calcium oxide and the mixture hot-pressed at 2100 C. and 4000 pounds per square inch thermoelectric elements are produced which exhibit Z factors of about 0.87 10' C. at 1200 C. as indicated in FIGURE 5. The same matrix material, with a boron nitride (4 mole percent) dispersant added, yields elements with merit factor of less than 0.74 10- C. at 1200 C., as shown in FIGURE 5. Thus, an increase of 17.5% in the Z factor results in this case through the use of calcium oxide homogeneously dispersed through a matrix (element 32 of FIGURE 3) of Mg-Al doped p type boron (89 mole percent)-carbon (11 mole percent) and beryllium dope n boron (89 mole percent) carbon (11 mole percent). The average spacing (element 30 of FIGURE 3) between particles of the dispersant in both matrices is 1000 A. and the particles of the dispersant (element 31 of FIGURE 3) range in size from S0 A. to 200,000 A.

When a thermoelectric cooling unit for use at elevated temperature and consisting of the above materials, equipped with junctions and leads such as

elements

21 and 22 of FIGURE 1 is connected in series with a power source, element 23 of FIGURE 1, the temperature difference between the hot and cold junctions, which is indicative of the cooling and heating capacities for the modified thermoelectric material is about 9% greater than for the case of the unmodified material.

Similarly, beneficial effects are attained when .001 mole percent to 29 mole percent of oxides, borides, phosphides, sulphides, silicides, carbides and nitrides are employed within the limits of particle size, interparticle spacing, melting point and solubility criteria specified above, together with the arithmetic deviation in percent cubic thermal expansion.

The percent cubic thermal expansion of the dispersants and matrix and the deviations between them at several temperatures are shown in the table below:

When thermoelectric elements are to be used over a large temperature differential, it is important to provide such elements with a gradation in properties along the path of energy fiow and particularly heat flow through such elements.

In this example, p type boron (89 mole percent)- carbon (11 mole percent) and n type boron (89 mole percent)-carbon (11 mole percent) matrices are modified with magnesium oxide, respectively.

Whether for cooling, heating or power generation, heat flow occurs from the hot zone to the cold zone through composite elements or legs 10 and 11 of FIGURE 2. For a case when a device of the configuration of FIGURE 2 is used to generate power, element 10 (as shown) consists of 3 segments;

elements

1, 2, and 3. For high efficiency of energy conversion, element 1 should have about the same merit factor as

elements

2 and 3. Likewise, element 6 of leg 11 has about the same merit factor as elements 7 and 8. For the case at hand, element 10 consists of a n type material while the polarity of element 11 is p type. Element of FIGURE 2 is an electrical and thermal contact between legs and 11 and the energy source, or hot zone. Element 4 serves as electrical and thermal contact for the cold side of the thermoelectric unit of FIGURE 2.

A superior generator is obtained when elements 10 and 11, consisting, respectively, of p and n type boron-carbon matrix materials are mechanically strengthened and thermoelectrically improved by dispersions of the above additive. The thermoelectric elements for this generator unit, similar in construction to that shown in FIGURE 2, are produced as follows:

Mechanical blends of fine particle (500 A. to 450,000 A.) of n type boron-carbon modified with fine particle magnesium oxide (100 A. to 350,000 A.) are produced. The blend for element 1 consists of a mixture of a nominal 12 mole percent magnesium oxide in n type boroncarbon. This powder blend is poured into the bottom of a boron nitride lined carbon mold, or compaction die, large enough to hold the powder charges for

elements

1, 2 and 3. Next a powder blend of nominal 7 mole percent magnesium oxide in the n type boron-carbon matrix (for element 2) is added on top of the 12 mole percent magnesium oxide/boron-carbon mix in the compaction die. Following this, a powder blend of a nominal 0.3 mole percent of magnesium oxide in the n type boron-carbon is placed on top (element 3) of the loose powder for element 2. The molecular ratio of elements 122:3 of leg 10 is approximately 0.5 1.5 1, respectively, for this example. Other molecular ratios for n type legs may be employed. Next, the compaction die is equipped with a male top and bottom ram to form a powder metallurgy hot-press type compaction-die assembly. This die assembly is then centered in an induction heating coil and the male rams connected with a means for applying pressure to them. A protective atmosphere of argon is provided for the die assembly and pressure equivalent to 4000 p.s.i. exerted on the loose powder. Upon heating to 2000 C. under the above pressure, compaction is completed in 5 minutes to produce a segmented type element or leg 10 of about 99% of theoretical density for the segments.

Element or leg 11 is produced in a similar manner from a matrix of p type boron-carbon (500 A. to 450,000 A.)

.modified by dispersed magnesium oxide powder (100 A.

to 350,000 A.). The same mole percents of magnesium oxide used for

elements

1, 2 and 3 are blended with the matrix material to produce

elements

6, 7 and 8 of leg 11. The same die materials, as well as compaction temperatures, pressures and other procedures are also used. The molecular ratios of

elements

6, 7 and 8 to each other are 0.5 1.5 1, respectively.

The hot electrical and thermal element 5 of the thermoelectric module shown in FIGURE 2 is attached to legs 10 and 11 by simultaneously bonding to element 5 during consolidation of the thermoelectric materials.

Elements

4 and 5, in this particular example consist of graphite. Element 4 is attached to the thermoelectric legs by the same technique.

Overall merit factors of 0.93X10 C. and

are obtained from segmented type legs 10 and 11, respectively, when such legs consisting of segments or

elements

1, 2, 3, 6, 7 and 8- are produced from the said matrix thermoelectric materials modified by homogeneous dispersions of the said refractory materials, and the units operated between 1100 C. and 1400 C. By comparison, the merit factors are 0.8 10 C. power and 0.75 X l0- C.

power, respectively, for legs 10 and 11 comprised of the same composition matrix materials modified by uniform dispersions of 14 mole percent of magnesium oxide, and operating over this same temperature range. Thus improvements of approximately 16% and 12% are obtained for matrices of n and p type boron-carbon, respectively, by the compositions, process and configurations of this example, using additives of the above specified range of the arithmetic deviation of cubic thermal expansion relative to the dispersant and the matrix.

Similar improvements of merit factors for various boron-carbon matrix compositions are obtained through practice of the technique of providing thermoelectric legs comprised of thermoelectric segments of different concentrations of dispersants of refractory particles. While only one refractory dispersant is used in a single thermoelectric matrix per leg in this example, each segment may be readily made of different dispersants. Other concentrations of dispersants than those described in this example are also used in the concentrations of such dispersants are maintained within the 0.001 mole percent to 29 mole percent range specified in this application. With regard to protective atmospheres used during fabrication, nitrogen, helium and even air can be used. Other electrically and thermally conductive materials may be substituted for graphite as

elements

4 and 5 of the typical device shown in FIGURE 2.

EXAMPLE 5 A process similar to that used in Example 4 is employed to fabricate elements 10 and 11 of FIGURE 2 to yield legs in which the thermoelectric properties of a single matrix are smoothly varied to produce legs which operate with higher merit factors over the same temperature drop than legs of constant or uniform composition. For example, continuously varied or gradated composition type legs 10 and 11 for the device shown in FIGURE 2 of this example are produced by feeding a continuously changing composition of magnesium oxide modified boron-carbon constituents into'a compaction die. In this manner, the lower portion of element 1 which is to be joined to element 5 of FIGURE 2 is comprised a 14 mole percent mixture of magnesium oxide with p type boron-carbon. The composition of the succeeding layers of blended powder fed into the compaction die to form element 1 is gradually decreased in magnesium oxide content until at the junction of elements 1 and 2 of FIGURE 2 the composition reaches 10 mole percent magnesium oxide to yield an average composition for element 1 of about 12 mole percent. The dispersed magnesium oxide content is then continuously decreased with increasing layers of powder charged into the die to form

elements

2 and 3 With smoothly gradated composition which average 7 mole percent; 0.3 mole percent magnesium oxide, respectively. The approximate molecular ratios of

elements

1, 2 and 3 of leg 10 are 0.5 :1.5 :1, as used in Example 4. Following charging of the powder to the die assembly in this way, compaction by pressure and elevated temperature proceeds as previously described in Example 4.

Elements

6, 7, and 8 of leg 11 are made in the same manner as are

elements

1, 2 and 3 of leg 10. Merit factors of 0.97 10 C. and 0.86 10- C. (n-type), respectively, are produced for legs 10 and 11 in a typical device configuration shown in FIGURE 2 using the smoothly gradated type elements of this example when the units of the type shown in FIG- URE 2 are operated at temperatures ranging from 1100 C. to 1400 C. By comparison, merit factors of and 0.75 X 10 C. are obtained for elements 10 and 11, respectively, comprised of -p" and n type boron-carbon materials modified by uniform dispersions of 14 mole percent magnesium oxide.

In accordance with known device technology, advantage can be taken of the improved merit factors possible with such smoothly gradated thermoelectric legs to produce more highly efiicient power generating and high temperature heating-cooling units by either cascading or segmenting typical n and p legs 10 and 11 described in Examples 4 and with thermoelectric materials capable of more efficient operation in temperature ranges beyond the scope of the boron-carbon matrix material-s of this invention.

The percent cubic thermal expansion for the matrix and dispersant of Examples 4 and 5 and the deviations between them at several temperatures are shown in the table below:

A specific example of typical results in producing superior thermoelectric materials and devices, through the inducement of strain at elevated temperatures into the lattice of the thermoelectric matrix material, so as to beneficially decrease the product of the electrical resistivity and thermal conductivity of such materials through the dispersion of refractory phase with higher expansion coeificients relative to the thermal expansion coefiicients of matrix materials, is shown by comparing the merit factor obtained for a boron-carbon thermoelectric matrix material (characterized by 1.86% expansion from 0 C. to 1200 C.) with 14 mole percent of magnesium oxide (characterized by a 5.34% expansion from 0 to 1200 C.) dispersed in it to the merit factor for the same composition boron-carbon matrix in which 14 mole percent of boron nitride (characterized by a 1.35% expansion from 0 C. to 1200 C.) is used as the dispersed phase. Individual thermoelectric elements, such as element 20 of FIGURE 1, produced under identical pressing conditions by incorporating the above quantities of MgO and BN in an identical matrix material when each of the individual thermoelectric elements is attached with proper leads (

elements

21 and 22 of FIGURE 1) toa measuring circuit 23, exhibit different merit factors when operated over the same temperature drop. Specifically, a merit factor of 0.9 C. at 1200 C. is obtained for the thermoelectric boron-carbon matrix material in which 14 mole percent magnesium oxide is homogeneously dispersed prior to hot pressing at 2000 C. and 4000 p.s.i. By comparison, an identical boron-carbon matrix composition in which 14 mole percent boron nitride is homogeneously blended prior to compacting into a test piece under identical temperatures and pressure fabrication conditions, as well as being fabricated with identical thermal and electrical contacts, exhibits a merit factor of only 0.8 10- C. at 1200" C.

The decrease in the merit factor for the matrix material modified with boron nitride as compared with the one in which magnesium oxide is dispersed is larger than could be accounted for by the relative thermal and electrical conductivities of the dispersants. The results obtained are more in line with the relative degree of the matrix lattice strain that is estimated from the ratio of the cubic expansion coeflicients of each dispersant used. That is, the thermoelectric properties of the matrix material are enhanced at high temperature when the coeflicient of expansion of the dispersant is greater than that for the matrix material, with high coeflicient dispersants yielding the greatest benefit to thermoelectric materials for use at elevated temperatures. Thus beneficial effects are obtained with p and n type materials of the present invention.

Use of dispersed phases of higher expansion coefficients than those of boron-carbon matrices permits employment of high-temperature flame and plasma spray apparatus to economically produce large area (high power) thermoelectric units in a variety of geometries and without the use of high forming pressures. Costly dies and die-heating apparatus are minimized as proper selection of the dispersed phase creates the beneficial lattice stress and strain effect desired.

The percent cubic thermal expansion of the dispersant and matrix, and deviation between them, at several temperatures are shown in the table below:

A specific example of the power producing characteristics of devices made in accordance with the present invention is shown when a simple thermoelectric device consisting of a modified matrix unit as described in Example 1 is equipped with electrical and thermal contacts,

elements

21 and 22 of FIGURE 1 and connected to a matched resistance load and powermeter. When an energy source is used to heat the hot junction of this unit to 1200 C. and a calorimetric heat sink provided to cool the cold junction of this unit to 400 C., 0.5 watts of electrical power output are produced for a heat power input of 13.5 B.t.u. per hour. By comparison, the power output of an unmodified matrix unit of the same cross sectional area of Example 1 is only 0.43 watt for the same heat power input. The advantage of the modified matrix material over the unmodified is a significant 16.3% increase in power generation capability, under the same temperature or thermal flux conditions.

What is claimed is:

1. As an article of manufacture, a shaped, semiconductor two-phase body comprising a matrix of consolidated boron and carbon in the proportion of between mole percent to mole percent boron and 25 mole percent to 5 mole percent carbon, the said matrix having dispersed therein a particulate material selected from the group consisting of the stable binary sulfides, oxides, borides, carbides, nitrides, silicides, and phosphides of boron, thorium, aluminum, magnesium, calcium, titanium, zirconium, tantalum, silicon, vanadium, hafnium, columbium, tungsten, iron, cobalt, nickel, rhenium, molybdenum, beryllium, barium and rare earths of the lanthanide and actinide series, the said dispersant being present in the range of from 0.001 mole percent to 29 mole percent of the matrix, and having an absolute melting point of at least of the melting point of the said matrix material, the said dispersant also having a solubility in the matrix of less than 10 mole percent at a temperature which is 60% of the absolute melting point of the matrix, the said dispersant also being characterized by a percent cubic thermal expansion which differs arithmetically from that of the matrix by a deviation of from 1.50% to 6.00% over the range of 0 C. to 1500 C.

2. A thermoelectric unit comprising at least one shaped, semiconductor two-phase body, and electrical leads at opposed portions of the said body, the said body comprising a matrix of a combination of between 75 mole percent to 95 mole percent of boron, and 25 mole percent to 5 mole percent of carbon and having dispersed within the said matrix, particles of calcium oxide present at from 0.001

mole percent to 29 mole percent of the matrix, the said calcium oxide dispersant being characterized by a solubility in the matrix of less than 10 mole percent at a temperature which is 60% of the absolue melting point of the matrix, and a percent cubic thermal expansion which differs arithmetically from that of the matrix by a deviation of from 1.50% to 6.00%, over the range of from C. to 1500 C.

3. A thermoelectric unit comprising at least one shaped, semiconductor two-phase body, and electrical leads at opposed portions of the said body, the said body comprising a matrix of a combination of between 75 mole percent to 95 mole percent of boron, and 25 mole percent to mole percent of carbon and having dispersed within the said matrix, particles of silicon nitride present at from 0.001 mole percent to 29 mole percent of the matrix, the said silicon nitride dispersant being characterized by a solubility in the matrix of less than mole percent at a temperature which is 60% of the absolute melting point of the matrix, and a percent cubic thermal expansion which differs arithmetically from that of the matrix by a deviation of from 1.50% to 6.00%, over the rang of from 0 C. to 1500 C.

4. A thermoelectric unit comprising at least one shaped, semiconductor two-phase body, and electrical leads at opposed portions of the said body, the said body comprising a matrix of a combination of between 75 mole percent to 95 mole percent of boron and 25 mole percent to 5 mole percent of carbon and having dispersed within the said matrix, particles of magnesium oxide present at from 0.001 mole percent to 29 mole percent of the matrix, the said magnesium oxide dispersant being characterized by a solubility in the matrix of less than 10 mole percent at a temperature which is 60% of the absolute melting point of the matrix, and a percent cubic thermal expansion which differs arithmetically from that of the matrix by a deviation of from 1.50 to 6.00% over the range of from 0 C. to 1500 C.

5. A thermoelectric unit comprising at least one shaped, semiconductor two-phase body, and electrical leads at opposed portions of the said body, the said body comprising a matrix of a combination of between 75 mole percent to 95 mole percent boron and 25 mole percent to 5 mole percent of carbon, and having dispersed within the said matrix, particles of magnesium oxide present at from 0.001 mole percent to 29 mole percent of the matrix, the said magnesium oxide dispersant also being characterized by a solubility in the matrix of less than 10 mole percent at a temperature which is 60% of the absolute melting point of the matrix, and a percent cubic thermal expansion which differs arithmetically from that the matrix by a deviation of from 1.50% to 6.00% over the range of from 0 C. to 1500 C., the proportion of the said dispersant differing in one region of the said body from the proportion thereof at another region of the said body.

6. A thermoelectric unit comprising at least one shaped, semiconductor two-phase body, electrical leads at opposed portions of the said body, the said body comprising a matrix of consolidated boron and carbon in the proportion of between 75 mole percent to 95 mole percent boron, and 25 mole percent to 5 mole percent carbon, the said matrix having dispersed therein a particulate material selected from the group consisting of stable binary sulfides, oxides, borides, carbides, nitrides, silicides, and phosphides of boron, thorium, aluminum, magnesium, calcium, titanium zirconium, tantalum, silicon, vanadium, hafnium, columbium, tungsten, iron, cobalt, nickel, rhenium, molybdenum, beryllium, barium and rare earths of the lanthanide and actinide series, the said dispersant being present in the range of from 0.001 mole percent to 29 mole percent of the matrix, and having an absolute melting point of at least 105% of the melting point of the said matrix material, the said dispersant also having a solubility in the matrix of less than 10 mole percent at a. temperature which is 60% of the absolute melting point of the matrix the said dispersant also being characterized by a percent cubic thermal expansion which differs arithmetically from that of the matrix by a deviation of from 1.50% to 6.00% over the range of from 0 C. to 1500" C.

7. A thermoelectric unit as described in claim 6 in which there is a gradation in concentration of the dispersed particulate additive material from the respective opposed regions to be subjected to heat and to cold.

8. Process for converting heat into electricity which comprises applying heat to a hot junction element in physical and electrical contact with a first leg, of p-type conductivity, and a second leg of n-type conductivity said legs and hot junction element forming a first thermoelectric junction, at least one of said legs being comprised of a matrix of consolidated boron and carbon in the proportion of between 75 mole percent to mole percent boron and 25 mole percent to 5 mole percent carbon, the said matrix having uniformly dispersed therein a particulate dispersant selected from the group consisting of stable binary sulfides, oxides, borides, carbides, nitrides, silicides, and phosphides of boron, thorium, aluminum, magnesium, calcium, titanium, zirconium, tantalum, silicon, vanadium, hafnium, columbium, tungsten, iron, cobalt, nickel, rhenium, molybdenum, beryllium, barium and rare earths of the lanthanide and actinide series series, the said dispersant being present in the range of from 0.001 mole percent to 29 mole percent of the matrix, and having an absolute melting point of at least of the melting point of the said matrix material, the said dispersant also having a solubility in the matrix of less than 10 mole percent at a temperature which is 60% of the absolute melting point of the matrix, the said dispersant also being characterized by a percent cubic thermal expansion which differs arithmetically from that of the matrix by a deviation of from 1.50% to 6.00% over the range of from 0 C. to 1500 C. cooling the cold junction element in physical and electrical contact with said first and second legs, remote from the said hot junction and forming a second thermoelectric junction, and withdrawing electricity from said cold junction.

9. Process of converting heat into electricity which comprises applying heat to a hot junction element in physical and electrical contact with a first leg, of p-type conductivity, and a second leg of n-type conductivity, said legs and hot junction element forming a first thermoelectric junction, at least one of said legs being comprised of a matrix of consolidated boron and carbon in the proportion of between 80 mole percent to 93 mole percent boron and 20 mole percent to 7 mole percent carbon, the said matrix having uniformly dispersed therein a particulate dispersant selected from the group consisting of stable binary sulfides, oxides, borides, carbides, nitrides, silicides, and phosphides of boron, thorium, aluminum, magnesium, calcium, titanium, zirconium, tantalum, silicon, vanadium, hafnium, columbium, tungsten, iron, cobalt, nickel, rhenium, molybdenum, beryllium, barium and rare earths of the lanthanide and actinide series, the said dispersant being present in the range of from 0.01 mole percent to 20 mole percent of the matrix, and having an absolute melting point of at least 105 of the melting point of the said matrix material, the said dispersant also having a solubility in the matrix of less than 10 mole percent at a temperature which is 60% of the absolute melting point of the matrix, the said dispersant also being characterized by a percent cubic thermal expansion which dilfers arithmetically from that of the matrix by a deviation of from 1.75% to 6.00% over the range of from 0 C. to 1500" C. cooling the cold junction element in physical and electrical contact with said first and second legs, remote from the said hot junction and forming a second thermoelectric junction, and withdrawing electricity from said cold junction.

10. Process for converting heat into electricity which comprises applying heat to a hot junction element in physical and electrical contact with a first leg, of p-type conductivity, and a second leg of n-type conductivity, said legs and hot junction element forming a first thermoelectric junction, at least one of said legs being comprised of a matrix of consolidated boron and carbon in the proportion of between 85 mole percent to 91 mole percent boron, and 15 mole percent to 9 mole percent carbon, the said matrix having uniformly dispersed therein a particulate dispersant selected from the group consisting of stable binary sulfides, oxides, borides, carbides, nitrides, silicides, and phosphides of boron, thorium, aluminum, magnesium, calcium, titanium, zirconium, tantalum, silicon, vanadium, hafnium, columbium, tungsten, iron, cobalt, nickel, rhenium, molybdenum, beryllium, barium and rare earths of the lanthanide and actinide series, the said dispersant being present in the range of from 0.1 mole percent to 15 mole percent of the matrix, and having an absolute melting point of at least 105% of the melting point of the said matrix material, the said dispersant also having a solubility in the matrix of less than 10 mole percent at a temperature which is 60% of the absolute melting point of the matrix, the said dispersant also being characterized by a percent cubic thermal expansion which differs arithmetically from that of the matrix by a deviation of from 2.00% to 6.00% over the range of from C. to 1500 C. cooling the cold junction element in physical and electrical contact with said first and second legs, remote from the said hot junction and forming a second thermoelectric junction, and withdrawing electricity from said cold junction.

11. The process for converting electricity into cooling and heating effects which comprises applying electricity to a cold junction element in physical and electrical contact with a first leg of p-type conductivity, and a second leg of n-type conductivity, said legs, and cold junction elements forming a first thermoelectric junction and said legs and a hot junction forming a second thermoelectric junction, at least one of said legs being comprised of a matrix of boron and carbon in the proportion of between 75 mole percent to 95 mole percent boron and 25 mole percent to mole percent carbon, the said matrix having dispersed therein a particulate material selected from the group consisting of stable, binary sulfides, oxides, borides, carbides, nitrides, silicides, and phosphides of boron, thorium, aluminum, magnesium, calcium, titanium, zirconium, tnatalum, silicon, vanadium, hafnium, columbium, 4

tungsten, iron, cobalt, nickel, rhenium, molybdenum, beryllium, barium and rare earths of the lanthanide and actinide series, the said dispersant being present in the range of from 0.001 mole percent to 29 mole percent of the matrix, and having an absolute melting point of at least 105 of the melting point of the said matrix material, the said dispersant also having a solubility in the matrix of less than 10 mole percent at a temperature which is of the absolute melting point of the matrix, the said dispersant also being characterized by a percent cubic thermal expansion which differs arithmetically from than of the matrix by a deviation of from 1.50% to 6.00% over the range of from 0 C. to 1500 0, thereby cooling the cold junction element in physical and eletcrical contact with said first and second legs, remote from the said hot junction and forming a second thermoelectric junction, and cooling the said cold junction.

References Cited UNITED STATES PATENTS 775,188 11/1904 Lyons et al 1365.4

885,430 4/1908 Bristol 136--5.4 1,019,390 3/1912 Weintraub 23209 1,075,773 10/1913 Ferra 1365.5 1,079,621 11/1913 Weintraub 1365 1,127,424 2/1915 Ferra 136-54 1,546,833 7/1925 Geiger 10644 1,658,334 2/1928 Holmgren 2525 16 1,897,214 2/1933 Ridgway 23208 2,109,246 2/1938 Boyer et al 106--44 2,152,153 3/1939 Ridgway 1365 2,412,375 12/1946 Wejnarth 252516 2,445,296 7/1948 Wejnarth 252516 X 2,946,835 7/1960 Westbrook 1365 2,955,145 10/1960 Schrewelius l365 3,051,767 8/1962 Fredrick 136-5 3,061,656 10/1962 Chappel 1365 3,087,002 4/ 1963 Henderson et a1. 1364 OTHER REFERENCES Condensed Chemical Dictionary, 6th ed., Reinhold Pub. C0., New York (1961).

Fuschillo, N. Proc. Phys. Soc. (London) vol. BLXV, page 896 (1952).

5 WINSTON A. DOUGLAS, Primary Examiner.

JOHN H. MACK, Examiner.

A. M. BEKELMAN, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,343,373 5eptember 26, 1967 Courtland M. Henderson et a 1 It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 5, line 18, "150 C." should read 1500 C. Column 6, line 53, "140 C." should read 1400 C. Column 7, line 59, "improvde" should read improved Column 8, line 27, "dope" should read doped Column 10, line 20, "used in" should read used if Column '1 line 3 "l.50 to 6.00%" should read 1.50% to 6,00% 1 lne 51, "from that the matrix" should read from that of the matrix Column 15, line 45,"tnatalum" should read tantalum M Signed and sealed this 25th day of Novemhvr 1969.

(SEAL) Attest:

WILLIAM E. SCHUYLER, JR.

Commissioner of Patents Edward M. Fletcher, Jr.

Attesting Officer

Claims

1. AS AN ARTICLE OF MANUFACTURE, A SHAPED , SEMICONDUCTOR TWO-PHASE BODY COMPRISING A MATRIX OF CONSOLIDATED BORON AND CARBON IN THE PROPORTION OF BETWEEN 75 MOLE PERCENT TO 95 MOLE PERCENT BORON AND 25 MOL PERCENT TO 5 MOLE PERCENT CARBON, THE SAID MATIX HAVING DISPERSED THEREIN A PARTICULATE MATERIAL SELECTED FROM THE GROUP CONSISTING OF THE STABLE BINARY SULFIDES, OXIDES, BORIDES, CARBIDES, NITRIDES, SILICIDES, AND PHOSPHIDES OF BORON, THORIUM, ALUMINUM, MAGNESIUM, CALCIUM, TITANIUM, ZIRCONIUM, TANTALUM, SILICON, VANADIUM, HAFNIUM, COLUMBIUM, TUNGSTEN, IRON, COBALT, NICKEL, RHENIUM, MOLYBDENUM, BERYLIUM, BARIUM AND RARE EARTHS OF THE LANTHANIDE AND ANTINIDE SERIES, THE SAID DISPERSANT BEING PRESENT IN THE RANGE OF FROM 0.001 MOLE PERCENT TO 29 MOLE PERCENT OF THE MATRIX, AND HAVING AN ABSOLUTE MELTING POINT OF AT LEAST 105% OF THE MELTING POINT OF THE SAID MATRIX MATERIAL, THE SAID DISPERSANT ALSO HAVING A SOLUBILITY IN THE MATRIX OF LESS THAN 10 MOLE PERCENT AT A TEMPERATURE WHICH IS 60% OF THE ABSOLUTE MELTING POINT OF THE MATRIX, THE SAID DISPERSANT ALSO BEING CHARACTERIZED BY A PERCENT CUBIC THERMAL EXPANSION WHICH DIFFERS ARTHMETICALLY FROM THAT OF THE MATRIX BY A DEVIATION OF FROM 1.50% TO 6.00% OVER THE RANGE OF 0*C. TO 1500*C.

2. A THERMOELECTRIC UNIT COMPRISING AT LEAST ONE SHAPED, SEMICONDUCTOR TWO-PHASE BODY, AND ELECTRICAL LEADS AT OPPOSED PORTIONS OF THE SAID BODY, THE SAID BODY COMPRISING A MATRIX OF A COMBINATION OF BETWEEN 75 MOLE PERCENT TO 95 MOLE PERCENT OF BORON, AND 25 MOLE PERCENT TO 5 MOLE PERCENT OF CARBON AND HAVING DISPERSED WITHIN THE SAID MATRIX, PARTICLES OF CALCIUM OXIDE PRESENT AT FROM 0.001 MOLE PERCENT TO 29 MOLE PERCENT OF THE MATRIX, THE SAID CALCIUM OXIDE DISPERSANT BEING CHARACTERIZED BY A SOLUBILITY IN THE MATRIX OF LESS THAN 10 MOLE PERCENT AT A TEMPERATURE WHICH IS 60% OF THE ABSOLUE MELTING POINT OF THE MATRIX, AND A PERCENT CUBIC THERMAL EXPANSION WHICH DIFFERS ARITHMETICALLY FROM THAT OF THE MATRIX BY A DEVIATION OF FROM 1.50% TO 6.00%, OVER THE RANGE OF FROM 0* C. TO 1500*C.